EP0317801B1 - Process for preparing soft integral polyurethane foam articles - Google Patents

Process for preparing soft integral polyurethane foam articles Download PDF

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Publication number
EP0317801B1
EP0317801B1 EP88118289A EP88118289A EP0317801B1 EP 0317801 B1 EP0317801 B1 EP 0317801B1 EP 88118289 A EP88118289 A EP 88118289A EP 88118289 A EP88118289 A EP 88118289A EP 0317801 B1 EP0317801 B1 EP 0317801B1
Authority
EP
European Patent Office
Prior art keywords
foaming
agent
component
constituent
blowing agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88118289A
Other languages
German (de)
French (fr)
Other versions
EP0317801A3 (en
EP0317801A2 (en
Inventor
Herbert Dr. Dipl.-Chem. Schaper
Reinhard Dr. Dipl.-Chem. Krässig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phoenix AG
Original Assignee
Phoenix AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Phoenix AG filed Critical Phoenix AG
Publication of EP0317801A2 publication Critical patent/EP0317801A2/en
Publication of EP0317801A3 publication Critical patent/EP0317801A3/en
Application granted granted Critical
Publication of EP0317801B1 publication Critical patent/EP0317801B1/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to a process for the production of moldings from polyurethane soft integral foam (for example headrests, armrests, soft rear spoiler) with a density of 0.3 to 0.8 g / cm3, in particular 0.3 to 0.6 g / cm3, by foaming the polyol component (A component) with the isocyanate component (B component) in the presence of a blowing agent (C component).
  • polyurethane soft integral foam for example headrests, armrests, soft rear spoiler
  • C component blowing agent
  • the object of the invention is therefore to produce PU soft integral foam articles which have a smooth paintable surface.
  • the A and B components should be more storage and aging resistant.
  • Halogenated hydrocarbons are, in particular, methylene chloride or mixtures of methylene chloride and fluorine-chlorohydrocarbons.
  • a mixture of methylene chloride and trichlorofluoromethane in a ratio of 1: 3 is used in particular.
  • the A component expediently has a natural air load of less than 5% by volume.
  • a component blowing agent-free polyol mixture (parts by weight) branched polyether (MG 4800) 100.0 1,4-butanediol 11.0 Triethylenediamine (33% dissolved in dipropylene glycol) 2.0 Black paste (25%, carbon black dispersed in polyol) 5.6
  • B component: MDI prepolymer with tripropylene glycol (MDI 4,4′-methylenediphenyl diisocyanate)
  • C component methylene chloride / trichlorofluoromethane (1: 3)
  • B component 30-34 ° C C component: RT (approx.

Abstract

A process for the production of mouldings from soft integral (structural) polyurethane foam (for example headrests, armrests and soft rear spoilers) having a density of from 0.3 to 0.8 g/cm<3>, in particular from 0.3 to 0.6 g/cm<3>, by foaming polyol components (component A) with the isocyanate component (component B) in the presence of a blowing agent (component C). The essential feature of this invention is that the blowing agent is added under high pressure in an amount of from 0.5 to 5% by weight, based on the total weight of components A, B and C, the blowing agent being admixed by one of the three process variants: Variant I: The blowing agent is admixed with component A just before atomisation, Variant II: The blowing agent is admixed with component B just before atomisation, Variant III: The blowing agent is admixed additively in the mixing head during atomisation.

Description

Die Erfindung betrifft ein Verfahren zum Herstellen von Formkörpern aus Polyurethan-Weich-Integralschaum (z.B. Kopfstützen, Armlehnen, weiche Heckspoiler) mit einer Dichte von 0,3 bis 0,8 g/cm³, insbesondere von 0,3 bis 0,6 g/cm³, durch Verschäumen der Polyolkomponente (A-Komponente) mit der Isocyanatkomponente (B-Komponente) in Gegenwart eines Treibmittels (C-Komponente).The invention relates to a process for the production of moldings from polyurethane soft integral foam (for example headrests, armrests, soft rear spoiler) with a density of 0.3 to 0.8 g / cm³, in particular 0.3 to 0.6 g / cm³, by foaming the polyol component (A component) with the isocyanate component (B component) in the presence of a blowing agent (C component).

Bezüglich der Herstellung von Formkörpern aus PU-Integralschaum gibt es zahlreiche veröffentlichte Arbeiten, wobei nun die bisherigen Entwicklungsarbeiten der Anmelderin auf diesem Gebiet im Rahmen einer übersicht aufgeführt werden.
   DE-A-24 61 521 DE-C-26 12 896
   DE-A-27 14 518 DE-C-28 19 037
   DE-A-27 18 173 DE-C-32 26 818
   DE-A-29 22 769
Bei der Herstellung von PU-Weich-Integratschaumartikeln beobachtet man öfters die Bildung einer porösen bzw. pickeligen Oberfläche, u.a. bedingt durch den hohen Treibmittelgehalt.There are numerous published works relating to the production of molded articles made of PU integral foam, and the applicant's previous development work in this area is now listed in an overview.
DE-A-24 61 521 DE-C-26 12 896
DE-A-27 14 518 DE-C-28 19 037
DE-A-27 18 173 DE-C-32 26 818
DE-A-29 22 769
In the production of PU soft integral foam articles, the formation of a porous or pimply surface is often observed, partly due to the high blowing agent content.

Aufgabe der Erfindung ist es daher, PU-Weich-Integralschaumartikel herzustellen, die eine glatte lackierfähige Oberfläche aufweisen. Zudem sollen die A- und B-Komponenten lagerungs- und alterungsbeständiger sein.The object of the invention is therefore to produce PU soft integral foam articles which have a smooth paintable surface. In addition, the A and B components should be more storage and aging resistant.

Diese Aufgabe wird nun erfindungsgemäß dadurch gelöst, daß das Treibmittel in Form einer separaten Zudosierung unter Hochdruck in einer Menge von 0,5 bis 5 Gew.-%, insbesondere 1 bis 2 Gew.-%, bezogen auf Gesamtmasse von A-, B- und C-Komponente zugesetzt wird, wobei die Treibmittelbeigabe nach einer der drei Verfahrensvarianten erfolgt:

Variante I:
Das Treibmittel wird der A-Komponente kurz vor der Verdüsung beigegeben.
Variante II:
Das Treibmittel wird der B-Komponente kurz vor der Verdüsung beigegeben.
Variante III:
Das Treibmittel wird bei der Verdüsung additiv im Mischkopf beigegeben.
This object is now achieved according to the invention in that the blowing agent in the form of a separate metering in under high pressure in an amount of 0.5 to 5% by weight, in particular 1 to 2% by weight, based on the total mass of A-, B- and C component is added, the blowing agent being added using one of the three process variants:
Variant I:
The blowing agent is added to the A component shortly before spraying.
Variant II:
The blowing agent is added to the B component shortly before spraying.
Variant III:
The blowing agent is added to the mixing head during spraying.

Als Treibmittel werden zweckmäßigerweise folgende Substanzklassen eingesetzt:

  • Halogenkohlenwasserstoffe;
  • Benzin, Ester und/oder Ether.
The following substance classes are expediently used as blowing agents:
  • Halogenated hydrocarbons;
  • Gasoline, ester and / or ether.

Als Halogenkohlenwasserstoffe kommen insbesondere Methylenchlorid oder Gemische aus Methylenchlorid und Fluor-Chlor-Kohlenwasserstoffen zum Einsatz. Dabei wird insbesondere ein Gemisch aus Methylenchlorid und Trichlorfluormethan im Verhältnis von 1 : 3 verwendet.Halogenated hydrocarbons are, in particular, methylene chloride or mixtures of methylene chloride and fluorine-chlorohydrocarbons. A mixture of methylene chloride and trichlorofluoromethane in a ratio of 1: 3 is used in particular.

Die A-Komponente weist zweckmäßigerweise eine natürliche Luftbeladung von weniger als 5 Vol-% auf.The A component expediently has a natural air load of less than 5% by volume.

Im folgenden werden zwei Versuchsreihen aufgeführt, wobei zunächst einmal die allgemeinen Versuchsbedingungen genannt werden.
A-Komponente:  treibmittelfreie Polyolmischung (Gew.-T) verzweigter Polyether (MG 4800) 100,0 Butandiol-1,4 11,0 Triethylendiamin (33-%ig in Dipropylenglycol gelöst) 2,0 Schwarzpaste (25-%ig, Ruß dispergiert in Polyol) 5,6
B-Komponente:  MDI-Prepolymer mit Tripropylenglycol (MDI = 4,4′-Methylendiphenyldiisocyanat)
C-Komponente:  Methylenchlorid / Trichlorfluormethan (1 : 3)
Rohstofftemperatur:   A-Komponente: 25 - 27°C B-Komponente: 30 - 34°C C-Komponente: RT (ca. 21°C)
Form:  Heckspoiler (schräg aufgestellt) Formtemperatur: 40°C Formvolumen: 3,6 l Formstandzeit: 8 min
Anlage:  Hochdruck-RIM-Anlage (Das Treibmittel wird in den Polyolstrom vor der Verdüsung mit Hochdruck eingespritzt zur Vorvermischung.) Förderleistung: 340 g/sec Two test series are listed below, the first being the general test conditions.
A component: blowing agent-free polyol mixture (parts by weight) branched polyether (MG 4800) 100.0 1,4-butanediol 11.0 Triethylenediamine (33% dissolved in dipropylene glycol) 2.0 Black paste (25%, carbon black dispersed in polyol) 5.6
B component: MDI prepolymer with tripropylene glycol (MDI = 4,4′-methylenediphenyl diisocyanate)
C component: methylene chloride / trichlorofluoromethane (1: 3)
Raw material temperature: A component: 25-27 ° C B component: 30-34 ° C C component: RT (approx. 21 ° C)
Shape: rear spoiler (inclined) Mold temperature: 40 ° C Mold volume: 3.6 l Mold life: 8 min
System: high-pressure RIM system (the blowing agent is injected into the polyol stream at high pressure before premixing for premixing.) Delivery rate: 340 g / sec

Versuchsreihe 1Test series 1

Ziel: Untersuchung des Einflusses des Mengenanteils an C-Komponente auf die OberflächeObjective: To investigate the influence of the amount of C component on the surface Mischungsverhältnis von A : B : C in Gew.-TMixing ratio of A: B: C in parts by weight C-Komponente (Gew.-%)C component (% by weight) OberflächeneigenschaftSurface property 100 : 55 : 17,8100: 55: 17.8 10,310.3 sehr pickeligvery spotty 100 : 55 : 15,5100: 55: 15.5 9,19.1 (sehr) pickelig(very) spotty 100 : 55 : 10,7100: 55: 10.7 6,56.5 pickeligspotty 100 : 55 : 7,5100: 55: 7.5 4,64.6 Pickeligkeit fast verschwundenSpottiness almost gone 100 : 55 : 5,3100: 55: 5.3 3,33.3 praktisch glattpractically smooth 100 : 55 : 2,5100: 55: 2.5 1,61.6 glattsmooth Natürliche Luftbeladung der A-Komponente (< 5 Vol.-%)
Einschußzeit: 5,3 bis 5,5 sec
Dichte des Artikels: 0,46 g/cm³Natural air loading of the A component (<5% by volume)
Shot time: 5.3 to 5.5 sec
Density of the item: 0.46 g / cm³

Versuchsreihe 2Test series 2

Ziel: Untersuchung des Einflusses anderer Größen (Einschußzeit, Luftbeladung, Dichte) auf die OberflächeObjective: To investigate the influence of other quantities (shot time, air load, density) on the surface Einschußzeit (sec)Shot time (sec) Luftbeladung (Vol.-%)Air loading (vol .-%) Dichte (g/cm³)Density (g / cm³) OberflächeneigenschaftenSurface properties 5,35.3 < 5<5 0,460.46 glattsmooth 5,35.3 2222 0,460.46 glattsmooth 5,35.3 3535 0,460.46 beginnende Pickelbildungbeginning pimples 4,84.8 3535 0,410.41 glattsmooth

Mischungsverhältnis von A : B : C in Gew.-T (100 : 55 : 2,7) C-Komponente: 1,7 Gew.-% (bezogen auf Gesamtmischung).Mixing ratio of A: B: C in parts by weight (100: 55: 2.7) C component: 1.7% by weight (based on the total mixture).

Gesamtergebnis:Overall result:

  • 1) Bei einem Anteil von Treibmitteln (C-Komponente) von 0,5 bis 5 Gew.-% erhält man eine glatte bzw. nahezu glatte Artikeloberfläche, wobei man die besten Oberflächeneigenschaften bei einem Anteil von kleiner 2 Gew.-% an Treibmittel erhält. Dies ist überraschend, da man bisher davon ausgegangen ist, daß bei der Herstellung von Artikeln aus PU-Weich-Integralschaum ein Anteil von 10 bis 15 Gew.-% Treibmittel erforderlich ist, um die gewünschte Dichte (insbesondere < 0,6 g/cm³) und Lackierbarkeit der Oberfläche zu erreichen. Geringere Mengen (< 10 Gew.-%) an Treibmitteln sind bisher nur bei der Herstellung von Formkörpern aus Polyurethan-Integralschaum mit einer Dichte von 0,9 g/cm³ (DE-C-28 19 037) sowie aus harten Polyurethan-Schaumstoffen im Rahmen des Niederdruck-Verfahrens (GB-A-1 209 456) zugesetzt worden.1) With a proportion of blowing agents (C component) of 0.5 to 5% by weight, a smooth or almost smooth article surface is obtained, the best surface properties being obtained with a proportion of less than 2% by weight of blowing agent . This is surprising since it has hitherto been assumed that in the production of articles made of PU soft integral foam, a proportion of 10 to 15% by weight of blowing agent is required in order to achieve the desired density (in particular <0.6 g / cm 3 ) and paintability of the surface. Smaller amounts (<10% by weight) of blowing agents have so far only been used in the production of molded articles from integral polyurethane foam with a density of 0.9 g / cm 3 (DE-C-28 19 037) and from hard polyurethane foams Low pressure process (GB-A-1 209 456) was added.
  • 2) Durch Variation der Einschußzeit kann bei hoher Luftbeladung die Oberflächeneigenschaft verbessert werden. Gleichzeitig wird die Dichte weiter erniedrigt.2) By varying the shot time, the surface property can be improved with a high air load. At the same time, the density is further reduced.
  • 3) Durch die separate Treibmittelzudosierung sind die A- und B-Komponenten lagerungs- und alterungsbeständiger.3) Due to the separate addition of blowing agent, the A and B components are more stable in storage and aging.

Claims (7)

  1. A method of production of mouldings from soft polyurethane integral foam of a density of from 0.3 to 0.8 g/cm³, especially 0.3 to 0.6 g/cm³, by foaming the polyalcohol constituent (A-constituent) with the isocyanate constituent (B-constituent) in the presence of a foaming-agent (C-constituent), characterized in that the foaming-agent is added under high pressure in the form of a separate metered addition in an amount of from 0.5 to 5 % by wt., especially 1 to 2 % by wt., referred to the total mass of A-, B- and C-constituents, the addition of foaming-agent being effected according to one of the three variants upon the method:
    Variant I :   The foaming-agent is added to the A-constituent shortly before the atomization;
    Variant II :   The foaming-agent is added to the B-constituent shortly before the atomization;
    Variant III :   The foaming-agent is added in the mixer head additively during the atomization.
  2. A method as in Claim 1, characterized in that halogen hydrocarbons are used as foaming-agent.
  3. A method as in Claim 2, characterized in that methylene chloride is used as foaming-agent.
  4. A method as in Claim 3, characterized in that fluoro-chloro-hydrocarbons are added to the methylene chloride.
  5. A method as in Claim 4, characterized in that a mixture of methylene chloride and trichlorofluoromethane in the ratio of 1:3 is used as foaming agent.
  6. A method as in Claim 1, characterized in that benzene, ester and/or ether are used as foaming-agent.
  7. A method as in one of the Claims 1 to 6, characterized in that the A-constituent exhibits a charge of natural air (< 5 % by vol.).
EP88118289A 1987-11-07 1988-11-03 Process for preparing soft integral polyurethane foam articles Expired - Lifetime EP0317801B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3737925 1987-11-07
DE3737925 1987-11-07

Publications (3)

Publication Number Publication Date
EP0317801A2 EP0317801A2 (en) 1989-05-31
EP0317801A3 EP0317801A3 (en) 1989-09-13
EP0317801B1 true EP0317801B1 (en) 1995-01-11

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EP88118289A Expired - Lifetime EP0317801B1 (en) 1987-11-07 1988-11-03 Process for preparing soft integral polyurethane foam articles

Country Status (3)

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EP (1) EP0317801B1 (en)
AT (1) ATE117004T1 (en)
DE (1) DE3852751D1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2058336C1 (en) * 1989-04-24 1996-04-20 Вильхельм Хютцен Ханс Polyurethane foam with volume weight not above 30 g/cm3 and a method of its producing
DE10203701C1 (en) * 2002-01-31 2003-12-04 Hennecke Gmbh Process for the production of polyurethane foam with adjustable cell structure

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1209456A (en) * 1967-04-19 1970-10-21 Baxenden Chemical Company Ltd Improvements relating to polyurethane foams
SE334737B (en) * 1970-01-21 1971-05-03 Ici Svenska Ab
DE3544914A1 (en) * 1985-12-19 1987-06-25 Elastogran Masch Bau DEVICE FOR PRODUCING A REACTION MIXTURE FROM AT LEAST TWO PLASTIC COMPONENTS

Also Published As

Publication number Publication date
EP0317801A3 (en) 1989-09-13
DE3852751D1 (en) 1995-02-23
EP0317801A2 (en) 1989-05-31
ATE117004T1 (en) 1995-01-15

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